US11643776B2 - Method for manufacturing a composition comprising microfibrillated cellulose - Google Patents
Method for manufacturing a composition comprising microfibrillated cellulose Download PDFInfo
- Publication number
- US11643776B2 US11643776B2 US16/977,159 US201916977159A US11643776B2 US 11643776 B2 US11643776 B2 US 11643776B2 US 201916977159 A US201916977159 A US 201916977159A US 11643776 B2 US11643776 B2 US 11643776B2
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- mfc
- fibers
- silicate
- alkali
- cellulose
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- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229920002678 cellulose Polymers 0.000 title claims description 27
- 239000001913 cellulose Substances 0.000 title claims description 27
- 239000000835 fiber Substances 0.000 claims abstract description 43
- 206010061592 cardiac fibrillation Diseases 0.000 claims abstract description 30
- 230000002600 fibrillogenic effect Effects 0.000 claims abstract description 29
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 23
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 17
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 14
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000123 paper Substances 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 5
- 239000011087 paperboard Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000004568 cement Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 description 14
- 229920003043 Cellulose fiber Polymers 0.000 description 12
- 239000000523 sample Substances 0.000 description 12
- 235000019353 potassium silicate Nutrition 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000002655 kraft paper Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 210000001724 microfibril Anatomy 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- 230000002255 enzymatic effect Effects 0.000 description 4
- 238000005243 fluidization Methods 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- -1 coatings Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000013074 reference sample Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- NVMMUAUTQCWYHD-ABHRYQDASA-N Asp-Val-Pro-Pro Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@H]1C(=O)N1[C@H](C(O)=O)CCC1 NVMMUAUTQCWYHD-ABHRYQDASA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920002522 Wood fibre Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000009996 mechanical pre-treatment Methods 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000002025 wood fiber Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 229920002201 Oxidized cellulose Polymers 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000002761 deinking Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013461 intermediate chemical Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 108700005457 microfibrillar Proteins 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940107304 oxidized cellulose Drugs 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000037039 plant physiology Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/007—Modification of pulp properties by mechanical or physical means
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/02—Cellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/08—Fractionation of cellulose, e.g. separation of cellulose crystallites
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/004—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives inorganic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
- D21D1/00—Methods of beating or refining; Beaters of the Hollander type
- D21D1/20—Methods of refining
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/04—Alkali metal or ammonium silicate cements ; Alkyl silicate cements; Silica sol cements; Soluble silicate cements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
Definitions
- the present invention relates to a method for manufacturing a composition comprising microfibrillated cellulose, a composition produced according to the method and the use thereof.
- MFC microfibrillated cellulose
- paper- and board making MFC may e.g. be used to increase the strength of the product to enable source reduction or to enhance retention.
- MFC may be used to provide reinforcement, to control dewatering or drying or to adjust rheological properties.
- MFC can further be used in a number of composite applications such as in adhesives, coatings, films, paints and packaging.
- MFC is usually produced from cellulose fibers by fibrillating the fibers by use of e.g. homogenization, microfluidization, grinding, refining or beating.
- Pre-treatment such as enzymatic, chemical or mechanical pre-treatment, is preferably used to reduce energy of fibrillation or to introduce functional groups and to adjust physical dimension of the MFC.
- WO2007091942 discloses a method for manufacturing MFC by enzymatic treatment followed by homogenization.
- MFC is produced by fibrillation of fibrous pulp in several steps at different consistencies.
- WO2011004284 discloses a process to produce MFC by simultaneous enzymatic and mechanical treatment.
- MFC metal-oxide-semiconductor
- aqueous suspensions with very low solid contents typically around 0.1-3 wt %.
- Transportation or processing (mixing, dewatering, drying, pumping) of MFC with such low solid contents is not sustainable or cost-efficient.
- the drying or dewatering of MFC to high solid contents may further deteriorate its properties e.g. cause wet hornification and change its performance.
- MFC forms a gel.
- a problem with an MFC gel is that mixing it into a composite, containing one or several other reactive chemicals, requires high intensity mixing and controlled reaction conditions.
- MFC is used as an active pre-cursor or as a reagent or carrier material, it is essential that the dosing is optimized to avoid competitive reactions or formation of by-products or other intermediate chemicals.
- One example of one such a reactive chemical is sodium silicate, which reaction with cellulose or modified cellulose requires controlled conditions.
- One example of this is the addition of low consistency MFC to process flows such as papermaking stock.
- the challenge connected to such addition is how to achieve flocculation, controlled interaction (such as quantitative retention) and an even distribution of the additives and components in the suspension and in the formed product thereof. Inadequate retention of additives may cause runnability and quality problems.
- WO2014132119 discloses a method for inline production of a retention agent.
- the patent describes polymerization of an aqueous silicate to colloidal silica in the presence of MFC.
- the MFC may be fed to the stock suspension separately to the feeding of the silicate and an acidic media or as a pre-mix.
- the invention discloses a method for manufacturing a composition, which method includes fibrillating fibers to form MFC in the presence of an alkali-metal silicate whereby an MFC and silicate mixture is formed.
- the alkali-metal silicate is preferably added to the fiber suspension prior to or during the fibrillation thereof.
- the presence of alkali-metal silicate during fibrillation of fibers to MFC reduces the viscosity and improves the dewatering efficiency, whereby the fibrillation can be accomplished at higher concentrations and a more uniform mixture of MFC-silicate is accomplished.
- the composition formed by the method of the invention may thus comprise higher solid contents than MFC produced according to conventional techniques usually does, whereby the transportation and processing of such a composition is more effective.
- the MFC-silicate mixture produced in accordance with the invention enables controlled addition of the components into process flows whereby undesired side reactions are avoided. It has further been shown, that the method of the invention prevents a strong MFC gel to be formed and facilitates the re-dispersing of MFC into water.
- the alkali-metal is preferably sodium silicate (water glass).
- Other alkali-metals may alternatively be used, such as calcium, potassium and/or lithium.
- sodium is preferred due to its cost-efficiency, reactivity and alkalinity.
- the fibrillation is preferably done to generate an MFC and silicate mixture having an SR (Schopper-Riegler) value of above 40, preferably above 50, or most preferably above 60.
- SR Schopper-Riegler
- the method may further include the step of mixing fibers with alkali-metal silicate prior to and/or during fibrillation.
- the fibers to be mixed with alkali-metal silicate and fibrillated have an SR value of between 15-80, preferably between 25-70 or between 35-70, prior to the steps of mixing and fibrillating.
- the method may comprise a step of pre-fibrillating the fibers before being mixed with the alkali-metal silicate. In this way, the process may be optimized and made more cost efficient.
- the method further comprises the step of dewatering the mixture to a solid content of at least 3 wt %, at least 5 wt %, at least 10 wt %, or even at least 15 wt % or at least 20 wt %.
- the final solid content further depends on the ratio silicate/MFC.
- silicate is present in an amount of at least 1-10 wt %
- the mixture is dewatered to solid content of e.g. between 3 wt %-20 wt %, or at least 5-20 wt % or 10-20 wt %, while in embodiments wherein silicate is present in higher amounts, the final solid content can also be higher.
- the initial pH i.e. the pH when the fibrillation process is started
- the pH is between 9.5-14 or 10-14, preferably between 10-13 during the fibrillation.
- the initial pH is below 5, such as in the range of 1-5.
- an acid may be added to the fiber suspension after the addition of water glass but before the fibrillation. In this way, the dewatering resistance is reduced even further.
- pigments such as calcium carbonate kaolin, bentonite, plastic pigments, starch pigments, nanoclays, PCC and/or talcum, are present during the fibrillation.
- an acidic media may be added to the MFC and silicate mixture whereby anionically charged colloidal particles are formed, which at least partly are precipitated on the MFC fibers.
- colloidal particles may be added as such or in combination with a cationic polymer to a process flow, e.g. a papermaking furnish.
- the acidic media may be any one of mineral acids such as sulphuric acids, phosphoric acids, hydrochloric acids; acidic metal salts such as polyaluminium chloride (PAC) and/or carbon dioxide.
- the acidic media is preferably added to lower the pH to below 9, or below 7 or below 6 or below 5 or even below 3.
- the pH may e.g.
- the temperature is further raised to at least 25° C., or at least 45° C. or at least 65° C. prior to or simultaneously as the treatment of the MFC and silicate mixture with an acidic media.
- the pH during fibrillation and after the acidification is dependent on the amount of water glass added and other co-additives in the suspension.
- the pH should be lowered by at least one or at least two units at the acidification of the MFC and silicate mixture.
- the invention discloses a composition produced by the method according to the invention.
- the invention discloses the use of the composition in paper or paperboard production.
- the composition comprising silicate-MFC may e.g. be added to the paper or paperboard furnish to enhance the strength of the thus produced paper or paperboard.
- the composition may further be added together with a cationic polymer to the paper or paperboard furnish to provide an efficient retention system.
- composition may also be used in cement production or in the production of composites for further use in e.g. adhesives, coatings, films, paints, detergents and packaging.
- adhesives, coatings, films, paints, detergents and packaging include as additive in deinking processes or in pulp beaching.
- cellulose fibers are fibrillated to form microfibrillated cellulose, which fibrillation is performed in the presence of an alkali-metal silicate.
- Microfibrillated cellulose shall in the context of the patent application mean a nano scale cellulose particle fiber or fibril with at least one dimension less than 100 nm. MFC comprises partly or totally fibrillated cellulose or lignocellulose fibers. The liberated fibrils have a diameter less than 100 nm, whereas the actual fibril diameter or particle size distribution and/or aspect ratio (length/width) depends on the source and the manufacturing methods.
- the smallest fibril is called elementary fibril and has a diameter of approximately 2-4 nm (see e.g. Chinga-Carrasco, G., Cellulose fibres, nanofibrils and microfibrils: The morphological sequence of MFC components from a plant physiology and fibre technology point of view, Nanoscale research letters 2011, 6:417), while it is common that the aggregated form of the elementary fibrils, also defined as microfibril (Fengel, D., Ultrastructural behavior of cell wall polysaccharides, Tappi J., March 1970, Vol 53, No. 3), is the main product that is obtained when making MFC e.g. by using an extended refining process or pressure-drop disintegration process.
- the length of the fibrils can vary from around 1 to more than 10 micrometers.
- a coarse MFC grade might contain a substantial fraction of fibrillated fibers, i.e. protruding fibrils from the tracheid (cellulose fiber), and with a certain amount of fibrils liberated from the tracheid (cellulose fiber).
- MFC cellulose microfibrils, fibrillated cellulose, nanofibrillated cellulose, fibril aggregates, nanoscale cellulose fibrils, cellulose nanofibers, cellulose nanofibrils, cellulose microfibers, cellulose fibrils, microfibrillar cellulose, microfibril aggregrates and cellulose microfibril aggregates.
- MFC can also be characterized by various physical or physical-chemical properties such as large surface area or its ability to form a gel-like material at low solids (1-5 wt %) when dispersed in water.
- the cellulose fiber is preferably fibrillated to such an extent that the final specific surface area of the formed MFC is from about 1 to about 300 m2/g, such as from 1 to 200 m2/g or more preferably 50-200 m2/g when determined for a freeze-dried material with the BET method.
- MFC multi-pass refining
- pre-hydrolysis followed by refining or high shear disintegration or liberation of fibrils.
- One or several pre-treatment step is usually required in order to make MFC manufacturing both energy efficient and sustainable.
- the cellulose fibers of the pulp to be supplied may thus be pre-treated enzymatically or chemically, for example to reduce the quantity of hemicellulose or lignin.
- the cellulose fibers may be chemically modified before fibrillation, wherein the cellulose molecules contain functional groups other (or more) than found in the original cellulose.
- Such groups include, among others, carboxymethyl (CM), aldehyde and/or carboxyl groups (cellulose obtained by N-oxyl mediated oxydation, for example “TEMPO”), or quaternary ammonium (cationic cellulose). After being modified or oxidized in one of the above-described methods, it is easier to disintegrate the fibers into MFC or nanofibrillar size fibrils.
- CM carboxymethyl
- TEMPO N-oxyl mediated oxydation
- quaternary ammonium cationic cellulose
- the nanofibrillar cellulose may contain some hemicelluloses; the amount is dependent on the plant source.
- Mechanical disintegration of the pre-treated fibers, e.g. hydrolysed, pre-swelled, or oxidized cellulose raw material is carried out with suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, ultrasound sonicator, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer.
- suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, ultrasound sonicator, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer.
- the product might also contain fines, or nanocrystalline cellulose or e.g. other chemicals present in wood fibers or in papermaking process.
- the product might also contain various amounts of micron size fiber particles that have not been efficiently fibrillated.
- MFC is produced from wood cellulose fibers, both from hardwood or softwood fibers. It can also be made from microbial sources, agricultural fibers such as wheat straw pulp, bamboo, bagasse, or other non-wood fiber sources. It is preferably made from pulp including pulp from virgin fiber, e.g. mechanical, chemical and/or thermomechanical pulps. It can also be made from broke or recycled paper.
- MFC cellulose nanofibril
- a suspension comprising cellulose fibers and an alkali-metal silicate is fibrillated.
- the alkali-metal silicate may be added to a suspension comprising cellulose fibers prior to or during fibrillation.
- the alkali-metal silicate may be added as a solution with a solid content of at least 5 wt % or at least 10 or at least 15 wt % to the fiber suspension.
- the cellulose fibers may be hardwood and/or softwood fibers.
- the fibrillation can be accomplished by use of e.g.
- a homogenizator preferably at a consistency of 1-4% by weight, in a super refiner, preferably at a consistency on of 1-10% by weight or by mechanical treatment in a compactor, shredder, refiner, defibrator, screw, pulper, pump, or high shear mixing devices, at a preferred consistency of between 5-30% by weight.
- the temperature is raised to above 30° C., or above 50° C. or preferably above 75° C. prior to or during the fibrillation.
- the method further comprise a pre-treatment step, prior to the fibrillating step, which pre-treatment step may comprise enzymatic or mechanical pre-treatment.
- sample 2-6 A trial series was performed in which the dewatering resistance of MFC containing compositions produced according to the invention (sample 2-6) were compared with reference MFC compositions (sample 1 and sample 7).
- Reference sample 1 is MFC made from 100 wt % kraf fibers, without the addition of water glass.
- Reference Sample 7 is a mixture of MFC made from kraft fibers and water glass, wherein the MFC and the water glass have been mixed after refining (post-mixing).
- Reference samples 2-6 are compositions according to the invention wherein kraft fibers have been fibrillated in the presence of water glass.
- the pH of the fiber suspensions were adjusted to approximately 9.5 before addition of sodium silicate.
- Water glass sodium silicate was added to the samples 2-6 prior to fibrillation.
- the water glass added was sodium silicate (Dry cont. 50.17 wt %, Be 48-50, Density 1.40-1.52 kg/dm3, SiO2, Na2O molar ratio 2-2.1).
- the process conditions prior and after fibrillation are shown in table 1.
- the amount of water glass added is calculated based on the total amount of fibers in the suspensions before fibrillation (20 means 20 wt % of the dry amount of fibers).
- the “pH, initial” refers to the pH after the addition of sodium silicate but prior to fibrillation.
- the pH was adjusted to 3.9 by the addition of sulphuric acid prior to the fibrillation.
- the fiber suspensions were fibrillated by fluidization. Fluidization was made by running the suspension 2 times through 400/200 micron chambers and then one time through a 200/100 micron chambers (Microfluidizer). No adjustment of the temperature was done before or after the trials.
- the reference MFC Sample 1, the Sample 4 of the invention and the reference post-mixing Sample 7 were mixed with bleached never-dried birch kraft pulp (unrefined) in accordance with Table 3, wherein TP 1 refers to a mixture of Sample 1 with kraft pulp, TP 4 refers to a mixture of Sample 4 with kraft pulp and TP 7 refers to a mixture of Sample 7 with kraft pulp.
- Pulp pads for centrifugation were formed using a vacuum filtration device equipped with a 0.65 ⁇ m DVPP filter.
- the cakes with approximately 7-15 wt % dry content were subjected to centrifugation and the water retention value was determined in accordance with SCAN-C 62:00. The results are shown in Table 3.
- FIG. 1 shows how the water retention value changes with increased MFC content for the different test points.
- WRV for the samples comprising 100 wt % MFC were calculated using extrapolation of the trendlines from the chart shown in FIG. 1 (Table 4).
- the water retention value of the compositions made in accordance with the invention are significantly lower than the water retention value of the references (TP4 and TP7), especially at higher MFC contents.
Abstract
Description
TABLE 1 | |||||||
Sample | 1 (ref) | 2 | 3 | 4 | 5 | 6 | 7 |
Kraft Fiber | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
[wt %] | |||||||
Water glass | 0 | 5 | 15 | 15 | 15 | 15 | 15 |
[wt %] | |||||||
Fluidization | 3x | 3x | 3x | 3x | 3x | 3x | 3x, |
post mixing | |||||||
pH, initial | 9.5 | 10.7 | 11.0 | 11.2 | 11.4 | 3.9 | |
PH, final | 7.09 | 10.64 | 10.81 | 11.27 | 11.39 | 3.8 | 11.01 |
Starting | 1.0 | 1.0 | 1.0 | 2.96 | 4.43 | 4.86 | 1.5 |
consistency | |||||||
[wt %] | |||||||
TABLE 2 | ||||||||
1 (ref) | 2 | 3 | 4 | 5 | 6 | 7 | ||
Filtration time, | 843 | 373 | 209 | 131 | 130 | 95 | 169 |
[Sec] | |||||||
(30 gsm) | |||||||
Dry content of | 25.90 | 26.23 | 24.57 | 27.15 | 26.78 | 27.23 | 26.44 |
drainage | |||||||
filter cake | |||||||
TABLE 3 | |||||
Approximate | |||||
Test | time of cake | ||||
Point | MFC, | WRV | forming, | ||
(TP) | [wt %] | [%] | [min] | ||
1 | 2.5 | 188 | 15 | ||
1 | 5.0 | 199 | 27 | ||
1 | 7.5 | 214 | 33 | ||
1 | 10.0 | 222 | 48 | ||
4 | 2.5 | 184 | 6 | ||
4 | 5.0 | 193 | 8 | ||
4 | 7.5 | 195 | 10 | ||
4 | 10.0 | 203 | 10 | ||
7 | 2.5 | 185 | 6 | ||
7 | 5.0 | 197 | 10 | ||
7 | 7.5 | 199 | 12 | ||
7 | 10.0 | 210 | 12 | ||
TABLE 4 | |||
TP | WRV [%)] | ||
1 | 646.02 | ||
4 | 409.50 | ||
7 | 492.00 | ||
Claims (12)
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PCT/IB2019/051288 WO2019166912A1 (en) | 2018-03-02 | 2019-02-18 | Method for manufacturing a composition comprising microfibrillated cellulose |
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